Alkylation process



Feb. 18, 1958 J. T. KELLY ET AL ALKYLATION PROCESS Filed April 50, 1956INVENTOR8= Jae T Kelly Human Ill. Knlgllf material containing complexedBF --hydrate and BF, are contacted in a closed vessel, the BF, partialpressure drops very rapidly at first and then United States Patent 12,824,151 ALKYLATION PROCESS Joe T. Kelly, Dickinson, and Harmon M.Knight, La Marque, Tex., assignors to The American Oil Company,

Texas City, Tern, a corporation of Texas Application April 30, 1956,Serial No. 581,506 14 Claims. (Cl. 260--683.44)

This invention relates to the reaction of isoparaffins or aromatichydrocarbons and olefins. More particularly it relates to the alkylationof isobutane with ethylene.

In the petroleum industry today, the octane race has placed a strain onfacilities and materials needed to make gasoline meeting present dayautomotive engine requirements. One of the remaining sources of highoctane components is the product of the alkylation of isobutane andethylene. This alkylation is not easy to carry out, particularly on alarge scale.

An object of the invention is the alkylation of isoparaflins,particularly isobutane, with olefins, particularly ethylene. Anotherobject is the alkylation of aromatic hydrocarbons with olefins. Otherobjects will become apparent in the course of the detailed description.

The alkylation of isoparaflins or aromatic hydrocarbons with olefins iscarried out in the presence of a novel catalyst pair. One member of thecatalyst pair is boron trifluoride. The other member of the catalystpair is a metal stannate hydrate, that is, a metal stannate saltcontaining water of hydration. Although the second component of thecatalyst pair is spoken of as a metal stannate hydrate, it is believedthat the solid member is more properly a complex of the hereinafterdefined metal stannate hydrate and BF the BF is believed to complex withsome or all of the hydrate water present in the metal stannate hydratesalt. More than the amount of BF needed to complex the water ofhydration is necessary to obtain the desired catalystic effect.

Boron trifluoride is one member of the catalyst pair. Commercial gradeanhydrous boron trifluoride is suitable for use as one member of thecatalyst pair.

The other member of the catalyst pair, hereinafter spoken of as thesolid member, is a metal stannate hydrate, i. e., a metal stannate saltcontaining water of hydration. The salt may be used as a fine powder, aspellets, or may be supported on a solid carrier such as alumina,charcoal, silica gel, etc. Not all metal stannates which contain waterof hydration are suitable, nor are all metal ions suitable. Theparticular metal ion components of the stannate salt hydrates arebismuth, cadmium, calcium, cobaltous, ferric, magnesium, manganous, andnickelous. In determining the efiective members, it has been consideredthat the catalyst pairs which did not product a yield, on a weightpercent basis on ethylene charged, when isobutane and ethylene werecontacted, of 100% or more, were unsuitable.

It is necessary that the above-defined metal stannate salts containhydrate water. The anhydrous salts do not have any promotional effect onthe activity of BF In those cases wherein a salt may exist in formshaving various amounts of water of hydration present, it is notnecessary that any particular hydrate be used. Apparently it isnecessary only that some water of hydration be present.

The BF;, and the defined salt react to form a solid When the saltgradually approaches a constant value. It appears that a very rapidreaction between the BF and some of the water of hydration takes place.This initially rapid re- 2,824,151 Patented Feb. 18, 195

action is then followed by a relatively slow reaction be: tween theremaining molecules of hydrate water and additional BF It appears thatwhen the salt hydrate is exposed to BF even in the presence ofhydrocarbon reactants, eventually all of the water of hydration willbecome associated with B1 on about a 1 mole of BF per mole of hydratewater basis.

A complex of the defined salt hydrate and BF, is not an effectivecatalyst for the alkylation in the absence of free-B1 Free-B1 is to beunderstood as BF existing in the reaction zone which is not complexedwith the defined metal stannate-hydrate. As soon as the salt hydrate hascomplexed with some BF the beneficial catalytic efiect exists. Thusfree-BF may exist in the reaction zone, as evidenced by the formation ofalkylate, even though all of the hydrate water has not been complexed.In a batch system, wherein less lBF is present than is theoreticallyrequired to complex all the water of hydration present in the salthydrate, eventually no alkylation will occur as charge is added, sinceall of the BF will become complexed.

In general, the process is carried out utilizing an amount of BF whichis in excess of that required to complex with all the hydrate waterpresent in the contacting zone, namely, in excess of about ll mole of BFper mole of hydrate water present. More than the minimum amount offree-BF is beneficial, in fact, the yield of alkylate increases rapidlywith increase in free- BF present, up to a maximum amount. The amount offree-B1 used is dependent somewhat upon the reactants themselves.However, when reacting isoparafllns and olefins, the free-BF usage isdesirably, set out on a BF to olefin weight ratio, of at least about0.2. In other words, at least about 0.2 lb. of free-BE; per 1b. ofolefin charged to the alkylation zone is desirable. About 1.5 parts byweight of BF per part of olefin charged appears to be about thedesirable maximum usage of BF It is preferred to use between about 0.35and 1 part by weight of free-3P per part by weight of olefin whenutilizing the lower molecular weight olefin, such as ethylene andpropylene.

The process may be carried out at any temperature below the temperatureat which the salt hydrate decomposes, that is, loss of all its water ofhydration. The temperatures of operation may be as low as 20 C. or evenlower. Temperatures as high as 150 C. and even higher may be used withsome of the salt hydrates which have relatively high decomposition.temperatures. More usually the temperature of operation will be betweenabout 0 C. and C. Lower temperatures appear to favor the formation ofthe hydrocarbons having 6 to 7 carbon atoms. It is preferred to operateat a temperature between about 25 C. and 40 C.

Sufiicient pressure is maintained on the system to keep a substantialportion of the hydrocarbons charged in the liquid state. The process maybe carried out at relatively low pressures, for example, 100 p. s. i.,or it may be carried out at elevated pressures, for example, 2000 p. s.i., or more. In general, pressures will be between about 200 and 1000 p.s. i. and preferably between abou 300 and 600 p. s. i.

The contacting of the isoparafiin or aromatic hydrocarbon and the olefinin the presence of the defined cata lyst pair is continued until anappreciable amount of alkylate has been formed. In batch reactions, itis possible to virtually extinguish the olefin, i. e., convertessentially 100% of the olefin by a sufiiciently long period ofcontacting. When operating in a continuous flow system, it may bedesirable to have a time of contacting such that substantial amounts ofolefins are not converted and obtain the complete conversion of theolefinby a recycle operation. The time of reaction will be determined bythe type of hydrocarbons charged, the ratio of isoparafiin or aromaticto olefin, the degree of mixing in the contacting zone and the catalystusage. A few tests will enable one to determine the optimum time ofcontacting for the particular system of operating conditions beingtried.

The reactants in the hydrocarbon charge to the alkylation process areisoparaflin, or aromatic and olefin. The olefin contains from 2 to about12 carbon atoms. Examples of suitable olefins are ethylene, propylene,butene-2, hexene and octene; in addition to these, the olefin polymersobtained from propylene and/ or butylene are also suitable for use inthe process, such as codimer, propylene trimer, propylene tetramer andbutylene trimer. It is preferred to operate with ethylene or propylene.

The aromatic hydrocarbons must be alkylatable by the particular olefinused. It is self-evident that an aromatic hydrocarbon which containsalkyl substituents positioned so that steric hindrance would prevent orgreatly reduce the possibility of alkylation with the particular olefinshould not be subjected to the process. Examples of particularlysuitable aromatic hydrocarbons are benzene, toluene, xylene,trimethylbenzenes, and the other alkyl analogues, such as propyl andbutyl; the naphthalene aromatic hydrocarbons, such as the mono anddisubstituted methylnaphthalenes. The isoparaffin reactant is defined asa parafiinic hydrocarbon which has a tertiary hydrogen atom, i. e.,paraflins which have a hydrocarbon atom attached to a tertiary carbonatom. Examples of these are isobutane, isopentane (2-methylbutane),2-methylpentane, Z-methylhexane, 3-mcthylhexane, 2,3,-dimethylbutane(di-isopropyl) and 2,4-dimethylhexane. Thus the isoparaffins usable asone reactant in the process contain from 4 to 8 carbon atoms.

In the isoparaffin-olefin system, the alkylation reaction is morefavored as the mole ratio of isoparaflin to olefin increases. Ingeneral, the isoparaffin to olefin mole ratio in the hydrocarbon chargeshould be at least 1. More than this amount is good and it is desirableto have an isoparaifin to olefin ratio between about 2 and 25 and insome cases more, for example, as much as 50. It is preferred to operatewith an isoparafiin to olefin mole ratio of between about and 15.

The presence of non-reactive hydrocarbons in the hydrocarbon charge isnot detrimental unless the reactants become excessively diluted. Forexample, the isoparafiin may also contain isomers of the normalconfiguration. The olefins may contain paralfins of the same carbonnumber. Mixures of 2 or more isoparafiins or 2 or more aromatichydrocarbons, or 2 or more olefins may be charged. In general, when aparticular product distribution is desired, it is preferable to operatewith a single isoparafin and a single olefin, for example, technicalgrade isebutane and ethylene, both of about 95% purity.

The reactants may be mixed together before they are charged into thereactor. Or, they may be charged into the reactor separately. Or, aportion of the olefin may be blended with the isoparafiin or aromaticbefore introduction into the reactor and the remainder of the olefininjected into the reactor. The charge may be introduced all at one pointinto reactor or it may be introduced at 2 or more points. The alkylationreaction is somewhat exothermic and temperature control is facilitatedby introducing the olefin into the reactor at more than one point.

The BF member of the catalyst pair may be premixed with the isoparaffinand olefin before introducing these into the reactor but this should notbe done when an extremely reactive system such as isobutanes andisobutylone or aromatic hydrocarbons and olefins are being used;

'or 'when an olefin that is very rapidly polymerizable is being used.The BF may be blended with the isoparaffin reactant and introduced intothe reactor with this member when the isoparafiin and the olefins arebeing introduced separately. The BB; may also be introduced directlyinto the reaction zone independently from the hydrocarbons charged. TheBF may be introduced into the reactor at a single point or at severalpoints to help control temperature and reaction rate.

The reactor may be a vessel providing a batch-type reaction, i. e., onewherein the desired amount of isoparaffin or aromatic and olefin arecharged to a closed vessel containing the catalyst pair and the vesselthen maintained at the desired temperature for the desired time. At theend of this time, the hydrocarbon product mixture and unreactedmaterials are withdrawn from the vessel and processed to separate thealkylate product from the unreacted materials and lower and highermolecular weight materials. The reactor may be a fixed bed operationwherein the reactants and free-B1 are flowed through the bed of thehydrate salt member of the catalyst pair, the space velocity beingcontrolled so that the desired amount of reaction is obtained during thepassage of the reactants through the bed of hydrate salt. Under someconditions, a moving bed of hydrate salt may be utilized. In stillanother set of circumstances, a fluidized bed of hydrate salt may beutilized with the incoming stream of reactants providing the energy forthe fluidization of the solid hydrate salt. Other methods of operationcommon in the catalytic refining aspects of the petroleum industryutilizing solid catalyst may be readily devised.

It has been pointed out that the solid member of the catalyst pair isreally a complex of the metal stannatesalt hydrate and BF the BFapparently reacting with the water of hydration. The complex may bepreformed,

' by exposing the salt hydrate to BF for a time sufficient to introducesome B 5 into the solid component or even enough to complex all of thewater of hydration; this being done before the reactants are introducedinto the reaction zone or even before the solid member of the catalystpair is positioned in the reaction zone. The complex may be formed insitu during a batch-type reaction. in the batch-type operation, it isconvenient to introduce all the B1 into the reaction vessel at once.This amount of B1 is sufficient not only to complex with the water ofhydration but also provide the desired amount of free-BR In a flowsystem, the solid member may be prepared in situ by charging freshhydrate salt to the reaction zone and forming the complex during theinitial passage of reactants and BF over the salt hydrate. Somealkylation reaction occurs even though the salt hydrate has not taken upsufficient BF to complex all the water of hydration. As the flow ofreactants and BF continues over the solid member, eventually the salthydrate will become saturated with respect to BB. At this time, theamount of BF introduced into the reaction zone should be cut back tothat amount of free-B1 desired, under this particular set of operatingconditions.

The illustrative embodiment set out in the'annexed figure forms a partof this specification. It is pointed out that this embodiment isschematic in nature, that many items of process equipment have beenomitted, since these may be readily added by those skilled in this artand that this embodiment is only one of many which may be devised, andthat the invention is not to be limited to this particular embodiment.

In this embodiment, it is desired to produce a high yield ofdi-isopropyl for use as a blending material for gasoline. Ethylene fromsource 11 is passed by way of line 12 into mixer 13. Liquid isobutanefrom source 14 is passed by way of lines 16 and 17 into mixer 13. Boththe ethylene and the isobutane are about purity, the remainder beingn-butane and ethane, with trace amounts of other components found inmaterials derived from petroleum refining sources. Mixer 13, in thisinstance,

is a simple orifice-type mixer suitable for intermingling a liguid. anda gas, or two liquids. Recycle isobutane from line 18 'is passed-by wayof line 17 into-mixer 13. In this embodiment, the molar ratioofis'obutane to *thylene'is 6.

From mixer '13, the blend of isobutane and :ethylene' is passedby way ofline 19, throughheat exchanger 21, where the temperature of'the blend isadjusted to 30 C. The temperature of the blend leaving exchanger "21 issomewhat lower than the reactionytemperature, since there is ,a heatrise in the reactor due to "exothermic reaction. From exchanger 21, the'streamfo'f isobutane and ethylene 'is passed byway of lines 22 and23into the top of reactor 24.

Boron trifluoride is passedlfromfsource 26by way of valved line 27andlinei28 into line 23, where it meets the. stream of isobutane andethylene. If desirable, a mixer may be introduced into line 23 to insurecomplete inter-mingling of the BB and the hydrocarbon charged.

"Recycle B'F is introduced from line '29 by way of lines 28 and 23. Inthis embodiment, the salt hydrate is completely complexed with respectto BF and only the necessary free-BE, is introduced by way of line 28.The weight .ratio of free-B1 from line 28 to ethylene present in line 23isll.

Reactor 24 is shown as a shell and tube type vessel. Hydrate salt iscontained in the tubes .31. The alumina balls 32 and 33 are positionedabove andflbelow the headers in the reactor to maintainthehydratesaltwithin the tubes. In order to maintain the temperature. inthe reactor at substantially 35 C., water is=introducedinto the shellside by way of line 36 andis. withdrawn by way of line 37.

In this embodiment, the reactor was charged with CoSnO .2H O. The,hydrate salt was preformed into pellets about one-eighth inch indiameter and about one eighth inch in height. Some silica was present toact as a lubricant in the extrusion of the pellets. The salt hydrate wascontacted with B1 in an, amount such that all of the water ofhydrationwas complexed with 8P This operation was carried out beforereactants were introduced into the reactor. The reactorp'ressure wasmaintained at "600 p. sui. This permits maintaining the isobutane andsubstantially all of the ethylene-in the liquid state.

The product hydrocarbon mixture is passed out of reactor 24 by way ofline 41. This streamcontains. the alkylate product, unreacted isobutane,a small amount of unreacted ethylene andpentanes as wellas BF The streamfrom line 41 is passed into gas separator 42 where the BF isobutane,some pentanes and some alkylate product are taken overhead by way ofline 43. The material taken overhead from the separator 42is-passed'into fractionator 44.

Fractionator 44 is adapted to separate theBF 'as ;a gas, the isobutaneas a liquid and the higher boiling materials as a bottoms product.Fractionator 44 is provided with an internal reboiler 46 and aninternalrcondensor 47. BF and unreacted ethylene are taken overhead fromfractionator 44 by way of line 48- and may be passed out of the systemby way of valved line 49. The material from line 49 may be-period'icallypassed to a BF purification operation to remove non-condensable inertgases which build up in the system. Ordinarily the stream from line 48is recycled by way of valved lines 29 and lines 28 and 23 to reactor 24.

isobutane is withdrawn as a liquid stream by way of line 51 and isrecycled by way of lines 18 and 17 to mixer 13 for reuse in the process.Bottoms product from fractionator 44 is withdrawn by way of line 52 andmay be passed to storage or further processing by way of valved line 53.This stream from line 52 consists.

Some unsaturated C hy-Q.

'andis adapted "to produce the'de'si'red alkylate'products from thehydrocarbon product mixture ente'ringffrom line 56. A vapor stream istaken overhead by way of linefil, is condensed in cooler 62a'n'd ispassed to storage by way of line63. :msterialfrom line 63 consistssubstantially of: isopehtahe and some unsaturated 0, material. Thismaterial "may he means a high octane blending stock for thep'ro'dubti'on of motor gasoline ofthedesiredvolatil'itycharacteristics.. l l d The alkylate product hereinis considered to bethat boiling above the pentane rang'e a'n'dboilingbelow the maximum temperature usable in moton'g'asol'ine. In general, a415 F. endpoinfla'lkylate :isblend'able into motor gasolinewithoutuadverse ieifectin fa specification calling for a 400 F. gasolineendpoint. Thus theal'kylate prodnet 'is considered lobe the materialboiling between about the lower limit Jofthe hexane ran e and 415 F. inthe ASTM distillation rocedure.

A considerable difference exists betwe'en'the octane number of the Cfraction of the "alkylate product and the higher boiling materiah. TliieC fraction, which boils from about 110 to 170 .F.,.has an F-l octanenumber of 101. The C-H- material has an octane number which rangesbetween about 75. and 85, depending somewhat on the fractionation.

Light alkylate, which includes all-the C material-and some of the Cmaterial, is withdrawn from tractionator 51 by way of line 66.Heavyalltylate, which includes most of theC and materialboilingup to415F. is,

withdrawn from fractionato'r -57 by way ofxline67. A small amountofhigher boilingwb'ottom's iswithdrawn by way of line "68.

In general, the C fraction of thealltylate product will contain fromabout 86 to about mole percent of diisopropyl (2,3-dimethy1butane).2-methylpentane and 3-inethy1pen'tane represent substantially theremainder of the C product. Generally, only trace amounts of n-- hexaneare present.

The results obtainable by the process of the instantin vention are setout in numerous illustrative runs below. These runs not only illustratethe types of metal sta'nnate hydrates which are suitable but alsoillustrate the effects. of change inoperating conditions.

In Tables I, II, and Ill, there are set out results in the testingofvarious'me'tal stannate hydrates by means of batch operation. In theseruns,1the tests were carried out under what are more or less standardconditions,\nar'nely, a. 4-liter carbon steel bomb was dried overnightin a stream of hot air at C. The stannate to betested (90 grams) wascharged to the bomb asa powder arid the bomb wasevacuated. Onekilogrambfa :dr'y blend of ethyleneand isobutane was added and then BE;(90 grams) was pressured l in. The charged bombs were placed in a rockerand allowed to rock for 20 hours. At the end of this time a liquidsample was drawn through a bomb containing activated alumina (to removedissolved BF and salt particles). This sample was submitted forPodbielniak distillation. A C cut from thePodbielniak distillation wasanalyzed by mass spectrometer. In some cases after sampling, theremaining major portion of the product was debntanized on an Oldershawcolumn and then fractionated on a packed column.- i j In Table I, dataare set-out showing the importance of water of hydration in the system.lnrun No. 1, the operation was carried out as described above exceptthat no saltwas present in the bomb. Theresillts sl'lb'w that only 34%of depentanized alkylate product was obtainedv by the use of BF alone asthe catalyst.

Run No. 2, carried out with nickelous stannate in the anhydrous form,produced no more alkylate than did BF in the absence of stannate. RunNo. 3, wherein nickelous stan- 8 RUN NO. 18 In Run No. 18, toluene wasreacted with ethylene using cobaltous stannate.3H O and BF; as thecatalyst pair. The reaction was carried out in a one gallon stirredBased on ethylenecharged.

nate.2H O and BF were present, produced a depentanized monel autoclave.To the autoclave were charged 1581 alkylate product yield of 139% basedon ethylene charged grams of C. P. toluene, 90 grams of the salt and 103and resulted in the conversion of 84% of the ethylene grams of BF;.,.Over a period of 4 hours, 153 grams charged. of technical grade ethylene(95% C were added to In Table No. II, there are set out the results oftesting the autoclave. The contents of the reactor were stirred variousmetal stannate hydrates. These data were obfor an additional half hourbefore settling and removal tained under the approximate standardconditions utilized of the hydrocarbon materials. The conditions andrein bomb work. These standard conditions are approxisults are set outin Table III. Infrared analysis of the mately: Isobutane-ethylene moleratio, 2.4; hydrocarethyltoluene fraction showed that the p o ct i tibubon/salt weight ratio, 11; BF lethylene weight ratio, 0.7; tron wasvery ditferent from equilibrium. The ethyl- 20 hours contacting time,temperature range, 20-35 C. toluene isomer drstribution was about: Qrto, and an initial pressure of about 350 p. s. i. g. These runs meta, 2 fP Thls dlsm'blltlon indlcates show that CoSnO .2H O is outstandingamongst the stanthat this particular catalyst pair 1s partrcularlysuitable nates h diff re ce between F Q 3H 0 d for the preparation ofethyltoluene when raw material Fe (SnO .3H O is surprising, Othereifective stannates for Productlon 0f Phthallc anhydl'lde IS the chlefare Bi (SnO .5H 0, CdSnO .3H O, CaSn0 .H O, Want- 7 MgSnO .3I-I O, MnSnO.3H O and NiSnO .2H 0. TABLE III Although mercuric stannate .xl-i Oappears to be ineffective as an alkylation catalyst, analysis of theproduct I tun No... 56 hydrocarbon mixture plus the high ethyleneconversion Mannate shows that this salt is an excellent ethylenepolymeriza- R H dm tion catalyst in conjunction with BF rl i e eil oursgf jhn a Pressure s. l. g 180-300 TABLE I Temperat re 0. Toluene/Salt(Weigh 17. 6 Presence of water of hydration Toluene/Ethylene (Molar)- a.a 30 BFslEthylene (Weight) 0. 7

Yields (on toluene converted): Run No 1 2 a m f l f g g} 2 rorna CS 00Green Btannate None N 01 N1Sn0a.2H=0 042+ Products (Wt. Percent) 14 9Toluene Converted 17.8 conditions; Ethylene Converted 30lsobutanegithylfne (llliolllafln 3.0 fi fifijj 3' 0:9 Infrared could notdistinguish between mono-butyl and dlethyl- Time, Hours 20 20 201119118- Temnemure, 0 25-35 15-25 25-35 Approximate-based 0 Pressure p-Pressure (Range), p. s. i. g..- 300 270-23.: 365480 Vve claim:Results: 1. An alkylation process comprising contacting (a) l gyg ggggfif l an alkylatable feed hydrocarbon from the class consist- Igexanes10 2; ing of (1) isoparaffin having from 4 to 8 carbon atoms 7+ "f and(2) aromatic hydrocarbon and (b) an olefin hav- Total 34 1 39 ing from 2to 12 carbon atoms, in the presence of a Ethylene C t d P L V 84catalyst comprising essentially (i) a metal stannate salt containingwater of hydration, the metal ion of said salt h Podlblelniak and'massspectrometer analyses, based on ethylene i g b i clasfs cfmslstmg ofbismuth, cadmlum, c arge ca CIIJIII co atous errrc magnesium manganousand t t 2 t$$ffi$ fiL$f hydra ewa er mckelous, and (1:) BF;,, said BFbeing present in an TABLE 11 Various stannate hydrates Run No. 4 5 6 7 a9 10 Metal Ion Present Barium" Beryl- Bis- Cadml- Calel- Cobalt Copperllum muth um 1+ um 2+ Moles of Water of Hydration 3 3 5 3 3 3 3 EthyleneConverted. Percent 51 89 77 79 45 Alkylate (Wt. Percent) Isopentane 12Hexanes- 23 20 38 43 48 66 61 01+- 17 99 e3 10 Total (05 Free) 40 20 137106 123 156 71 Run No r 11 12 1.. 14 15 1e 17 Metal Ion Present FerrousFerric Mercury Magnesl- Manga- Nickel Lead um neseMolesofWaterofHydratlom- 3 -.3 a: 3 3 2 2 Ethylene Converted, Percent-32 94 100 88 69 84 51 Alkylate (Wt. Percent) Isopentane, 15 15 22Hexanes -l a1 99 9 75 47 27 29 1 11 so 1 47 52 5s 52 22 Total (0| Free)42 179 56 127 139 amount in excess of about 1 mole per mole of water ofhydration in said salt, at a temperature between about 30 C. and atemperature substantially below the temperature at which said hydratesalt decomposes, and at a pressure sufiicient to maintain a substantialportion of said reactants in the liquid state, and separating ahydrocarbon product mixture containing alkylate product of said feedhydrocarbon and said olefin.

2. An alkylation process wherein an isoparafiin having from 4 to 8carbon atoms and an olefin having from 2 to 12 carbon atoms arecontacted, in a molar ratio of isoparaflin to olefin between about 2 and50, at a temperature between about 20 C. and 150 C. and a pressurebetween about 100 and 2000 p. s. i., said pressure being at leastsulfcient to keep a substantial portion of said reactants in the liquidstate, for a time suflicient to permit an appreciable amount ofalkylation reaction to take place, in the presence of a catalystcomprising essentially (i) a metal stannate salt containing water ofhydration, the metal ion component being selected from the classconsisting of bismuth, cadmium, calcium, cobaltous, ferric, magnesium,manganous and nickelous, and (ii) boron trifiuoride, said BF; beingpresent in an amount in excess of one mole per mole of hydrate Waterpresent in said salt, removing a product hydrocarbon mixture from saidcontacting zone and an alkylate hydrocarbon product is separated fromsaid mixture.

3. The process of claim 2 wherein said isoparafiin is isobutane.

4. The process of claim 2 wherein said isoparaflin is diisopropyl.

5. The process of claim 2 wherein said olefin is ethylene.

6. The process of claim 2 wherein said olefin is propylene tetramer.

7. The process of claim 2 wherein said salt is bismuth stannate.

8. The process of claim 2 wherein said salt is nickelous stannate.

9. The process of claim 2 wherein said salt is cobaltous stannate.

10. The process of claim 2 wherein said temperature is between about 25C. and C.

11. The process of claim 2 wherein the BF is present in an amount, inexcess of 1 mole per mole of hydrate water, such that the free-BF toolefin weight ratio is between about 0.2 and 1.5.

12. An alkylation process which comprises contacting isobutane andethylene in a molar ratio of isobutane to ethylene between about 2 and25 at a temperature between about 20 C. and C. at a pressure betweenabout 200 and 1000 p. s. i., said pressure being suficient to keep asubstantial portion of said reactants in the liquid state for a timesuflicient to permit an appreciable amount of alkylation reaction totake place, in the presence of a catalyst pair comprising essentially(a) a salt-BF; complex consisting of a metal stannate salt containingwater of hydration, the metal ion component being selected from theclass consisting of bismuth, cadmium, calcium, cobaltous, ferric,magnesium, manganous and nickelous, and about 1 mole of BF per mole ofhydrate water present in said salt and (b) boron trifiuoride in anamount such that the weight ratio of free-B1 to ethylene charged is atleast about 0.2, removing product hydrocarbon mixture containingalkylate product from said contacting zone and separating alkylatehydrocarbon product from unreacted isobutane and ethylene.

13. The process of claim 12 wherein said temperature is between 25 C.and 40 C.

14. The process of claim 12 wherein said free-BFJ ethylene weight ratiois between about 0.35 and 1.

No references cited.

1. AN ALKYLATION PROCESS COMPRISING CONTACTING (A) AN ALKYLATABLE FEEDHYDROCARBON FROM THE CLASS CONSISTING OF (1) ISOPARAFFIN HAVING FROM 4TO 8 CARBON ATOMS AND (2) AROMATIC HYDROCARBON AND (B) AN OLEFIN HAVINGFROM 2 TO 12 CARBON ATOMS, IN THE PRESENCE OF A CATALYST COMPRISINGESSENTIALLY (I) A METAL STANNATE SALT CONTAINING WATER OF HYDRATION THEMETAL ION OF SAID SALT BEING FROM THE CLASS CONSISTING OF BISMUTH,CADMIUM, CALCIUM, COBALTOUS, FERRIC, MAGNESIUM, MANGANOUS AND NICKELOUS,AND (II) BF3, SAID BF3 BEING PRESENT IN AN AMOUNT IN EXCESS OF ABOUT 1MOLE PER MOLE OF WATER OF HYGRATION IN SAID SALT, AT A TEMPERATUREBETWEEN ABOUT -30*C. AND A TEMPERATURE SUBSTANTIALLY BELOW THETEMPERATURE AT WHICH SAID HYDRATE SALT DECOMPOSES, AND AT A PRESSURESUFFICIENT TO MAINTAIN A SUBSTANTIAL PORTION OF SAID REACTANTS IN THELIQUID STATE, AND SEPERATING A HYDROCARBON PRODUCT MIXTURE CONTAININGALYLATE PRODUCT OF SAID FEED HYDROCARBON AND SAID OLEFIN.